Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/42—Separation; Purification; Stabilisation; Use of additives
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
  • C07C55/02—Dicarboxylic acids
  • C07C55/14—Adipic acid
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
  • C07C51/14—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on a carbon-to-carbon unsaturated bond in organic compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/42—Separation; Purification; Stabilisation; Use of additives
  • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/584—Recycling of catalysts

Definitions

• the present invention relates to a process for the hydroxycarbonylation of pentenoic acids for the preparation of adipic acid, in the presence of a catalyst which is at least partly separated from the reaction mixture obtained after the hydroxycarbonylation and reused in a hydroxycarbonylation operation.
• adipic acid One of the most promising processes for the preparation of adipic acid consists in hydroxycarbonylating one or more pentenoic acids, in particular pentene-3-oic acid and pentene-4-oic acid, using carbon monoxide and water, in the presence of a catalyst based on iridium, rhodium or their mixtures and an iodinated promoter. Generally the reaction is carried out in the liquid phase at a temperature of 50 ° C to 300 ° C and under a partial pressure of carbon monoxide of a few bars. To consider the industrial use of a process of this type, it is obviously essential to be able to recycle at least part of the expensive catalyst used.
• the present invention specifically relates to a method comprising such recycling.
• the distillation of the most volatile compounds of the reaction mixture resulting from the hydroxycarbonylation allows the catalyst to remain with the diacids formed. Subsequent distillation of these diacids at low vapor pressure makes it necessary to subject them, as well as the catalyst, to prolonged heating at relatively high temperature, capable of degrading them and rendering the catalyst partially or completely inactive.
• the crystallization technique requires ensuring sufficient heat transfer and making it possible to obtain crystals of size required to be wrung out.
• the maximum level of solids is limited to a higher value of the order of 30 to 40%. All this leads to a large volume of equipment and to the immobilization of too large a quantity of very expensive catalyst.
• the present invention proposes to solve the problem of separation and recycling of the catalyst in the context of a hydroxycarbonylation process of pentenoic acids to adipic acid, by the use of the refining technique.
• pentenoic acid is meant in the context of the invention pentane-2-oic acid, pentene-3-oic acid, pentene-4-oic acid and their mixtures.
• Pentene-3-oic acid pns individually or in admixture with its isomers is more particularly suitable, because of its accessibility and the satisfactory results to which it leads during its hydroxycarbonylation.
• the catalyst used for the hydroxycarbonylation reaction can be based on rhodium, iridium or these two metals.
• Any source of rhodium or iridium can be used.
• the catalysts based on iridium which are more particularly suitable are: [IrCl (cod)] 2 , Ir 4 (CO) 12 and Ir (acac) (CO) 2 .
• Catalysts based on iridium or based on iridium and rhodium are particularly preferred within the framework of the process of the invention.
• the amount of catalyst to be used can vary within wide limits.
• the concentration of iridium and / or rhodium is between 5.10 -4 and 10 -2 mole / liter.
• iodinated promoter in the context of the process of the invention HI and the organo-iodinated compounds capable of generating HI under the reaction conditions and more particularly alkyl iodides having 1 to 10 carbon atoms. Methyl iodide is more particularly recommended.
• the amount of iodinated promoter to be used is generally such that the molar ratio I / Ir (and / or Rh) is greater than or equal to 0.1. It is not desirable for this ratio to exceed 20. Preferably the molar ratio I / Ir (and / or Rh) is between 1 and 5.
• the presence of water is essential for the conduct of hydroxycarbonylation.
• the amount of water to be used is such that the water / pentenoic acid molar ratio is between 0.01 and 10.
• the water / pentenoic acid molar ratio in the reaction mixture can be instantaneously lower than the minimum value indicated above, if one proceeds for example to the continuous injection of water, rather than to its introduction with the other fillers before the hydroxycarbonylation reaction.
• the water / pentenoic acid molar ratio is between 0.01 and 1, the previous remark concerning the minimum value also being valid.
• the hydroxycarbonylation reaction can be carried out either in a third solvent or in a large excess of pentenoic acids.
• a third solvent it is possible in particular to use saturated or aromatic aliphatic carboxylic acids containing a maximum of 20 carbon atoms provided that they are liquid under the reaction conditions.
• carboxylic acids mention may be made of acetic acid, propionic acid, butyric acid, valeric acid, adipic acid, benzoic acid and phenylacetic acid.
• the third solvent can also be chosen from saturated aliphatic or cycloaliphatic hydrocarbons and their chlorinated derivatives and aromatic hydrocarbons and their chlorinated derivatives, provided that these compounds are liquid under the reaction conditions.
• solvents that may be mentioned include benzene, toluene, chlorobenzene, dichloromethane, hexane and cyclohexane.
• the third solvent represents for example from 10% to 99% by volume relative to the total volume of said reaction mixture and preferably from 30% to 90% by volume.
• the hydroxycarbonylation reaction is carried out in the pentenoic acids themselves, that is to say pentene-2-oic acid, pentene-3-oic acid, pentene acid. 4-oic and their mixtures.
• the hydroxycarbonylation reaction is carried out under a pressure higher than atmospheric pressure and in the presence of carbon monoxide.
• the reaction is carried out in the liquid phase.
• the temperature is generally between 100 ° C and 240 ° C and preferably between 160 ° C and 200 ° C.
• the total pressure can vary within wide limits.
• the partial pressure of carbon monoxide, measured at 25 ° C. is generally from 0.5 bar to 50 bars and preferably from 1 bar to 25 bars.
• the reaction mixture resulting from the hydroxycarbonylation reaction essentially comprises the unprocessed pentenoic acids, water, the iodized promoter, the catalyst, the solvent optionally used, the adipic acid obtained, the other by-products formed in amounts. more or less important, such as for example 2-methyl glutaric acid, 2-ethyl succinic acid, valeric acid or gamma-valerolactone (or 4-methyl butyrolactone).
• This reaction mixture is subjected to a refining operation, either as it is, or preferably after a concentration operation, consisting in removing, in particular by distillation, part or all of the third solvent, if such a solvent has been used, or part of the excess pentenoic acids when the reaction was carried out without a third solvent.
• a concentration operation consisting in removing, in particular by distillation, part or all of the third solvent, if such a solvent has been used, or part of the excess pentenoic acids when the reaction was carried out without a third solvent.
• Refining in the present text is defined as the direct crystallization of the reaction mixture, preferably concentrated, on a cooled wall, on which the raffinate (essentially adipic acid) is deposited, while the remaining liquid is concentrated in the other constituents of the treated mixture, including the catalyst.
• the deposited crystal lattice retains by capillarity or inclusion a limited amount of the residual liquid.
• This technique is also known under the name of crystallization in a molten medium.
• the main objective of refining is to separate most of the adipic acid from the catalyst which remains essentially in the liquid residue (withdrawal); for this, an apparatus is chosen having a high ratio of heat exchange surface area / volume of reaction mixture to be treated, so as to limit the crystallization time of the raffinate and especially the amount of reaction mixture and allow a crystallization rate which can exceed 70 %.
• the refining operation can be described in the following general manner.
• the reaction mixture to be treated is introduced into the apparatus, at an initial temperature at least equal to the crystallization temperature of the mixture and, preferably, between this temperature and the temperature at which the hydroxycarbonylation reaction was carried out; the device itself is also at this temperature.
• This initial temperature is generally between 100 ° C and 200 ° C.
• the first phase of the operation consists in the progressive crystallization of adipic acid on the walls of the device. This crystallization is obtained by a programmed decrease in the temperature of the heat exchange walls, in particular using a heat transfer fluid circulating on the other side of said walls.
• the temperature decrease may be more or less rapid, depending on whether the mixture to be treated crystallizes in a relatively thin layer when it does not fill the entire volume of the device, or whether it crystallizes in forming a thick layer when the charged mixture is stationary and fills the entire volume of the device.
• the final temperature reached is limited by the melting temperature of the eutectic of the various constituents of the reaction mixture. It will be chosen according to the composition of the reaction mixture to be refined and the amount of adipic acid which it is desired to crystallize. In general, the lower this temperature, the more certain other constituents of the reaction mixture can contaminate the adipic acid crystals; conversely, the higher this temperature, the lower the recovery rate of adipic acid in the raffinate.
• the final temperature is generally set between 0 ° C and 70 ° C.
• the draining fraction enriched in catalyst and depleted in adipic acid relative to the reaction mixture treated, is recovered by pouring from the bottom of the apparatus. This constitutes the draining phase.
• the third phase of the refining operation consists in washing the crystals deposited on the walls of the apparatus, so as to recover most of the dripping liquid still retained on said crystals. It is carried out by reheating, at a variable speed depending on the type of industrial production, the crystals deposited, which causes their partial melting; thus there is drainage and replacement on the crystals of the draining liquid by a liquid much richer in adipic acid.
• This phase is called the penetrant phase. Its quantitative importance depends on the quantity of catalyst which it is desired to recover and conditions the purity and the recovery rate of adipic acid.
• the bleeding fraction can be combined with the fraction obtained during the draining phase or be subjected to another operation of separation of its constituents by any technique, in particular by refining.
• withdrawal in this text designates the part of the reaction mixture separated during the draining phase and / or the bleeding phase.
• the temperature to which the raffinate is brought during the penetrant phase varies according to the quantity of catalyst which it is desired to recover or the quantity of purified adipic acid which it is desired to obtain.
• This temperature is generally between the final temperature of the draining phase and 150 ° C. Preferably it is between 100 ° C and 145 ° C.
• the raffinate deposited on the walls of the apparatus can then be recovered by rapid melting of the crystals.
• the duration of the refining cycle can vary from approximately 1 hour to 30 hours, depending on the industrial technology adopted; thus a dynamic thin layer system, offering a large heat exchange surface relative to the volume to be treated, will require a much shorter duration than a static thick layer system.
• the withdrawal containing at least part of the catalyst, of the iodized promoter, of the unprocessed pentenoic acids as well as more or less significant amounts of the various constituents of the reaction mixture treated, can be directly recycled in a hydroxycarbonylation reaction (in particular the fraction drainage), or be previously subjected to one or more separation operations, aimed at separating the catalyst from all or part of the other constituents (in particular the penetrant fraction).
• This additional separation can itself be achieved by the refining technique; but it can be carried out by any other conventional technique, such as for example crystallization, distillation, extraction.
• the raffinate containing mainly adipic acid as well as catalyst and more or less significant amounts of the various constituents of the treated reaction mixture, can itself be subjected to one or more additional separation operations, in order to separate the catalyst and the iodine promoter it contains.
• this additional separation can itself be carried out by the refining technique; but it can be carried out by any other conventional technique, such as for example crystallization, distillation, extraction.
• the catalyst and the iodinated promoter thus separated can then optionally be recycled.
• the refining is carried out in such a way that at least 40% of the catalyst present in the reaction mixture to be treated is separated and preferably at least 80%.
• a preferred embodiment of the invention consists in carrying out a refining operation, during which at least 80% of the catalyst is separated, between an initial temperature between 100 ° C and 200 ° C and a final temperature for the phase of draining between 20 ° C and 60 ° C, the temperature then being raised between 100 ° C and 145 ° C for the PT phase; this refining operation is optionally followed by one or more other separation operations carried out on some or all of the fractions obtained, in order to separate the rest of the catalyst on the one hand and at least part of the branched diacids on the other hand.
• the catalyst thus obtained during refining is recycled in the hydroxycarbonylation reaction.
• butadiene its most generally usable derivatives are 3-butene-2-ol, 2-butene-1-ol, their mixtures and their carboxylic esters, in particular acetates, propionates, valerates, adipates and pentenoates.
• the autoclave connected to the pressurized gas supply, is hermetically sealed. 2 bar (0.2 MPa) of CO are admitted cold and the mixture is heated to 185 ° C. in 20 minutes by means of an electric heating collar. When this temperature is reached, the pressure is regulated to 20 bar (2 MPa).
• the kinetics of the reaction are monitored, by the absorption of CO in a reserve connected to the reactor, the pressure in the autoclave remaining constant.
• reaction time 30 min, corresponding to the total consumption of the water introduced, the reaction is stopped by cooling the reaction mixture.
• the autoclave is degassed and the reaction mixture is drawn off in the liquid state at 120 ° C.
• the reaction mixture is analyzed by vapor phase chromatography and by high performance liquid chromatography.
• the linearity rate expressed as the percentage ratio of A1 formed on all of the diacids A1, A2 and A3 formed, is 82%.
• reaction rate (calculated over 20 min of CO absorption) is 5.4 moles of CO absorbed per hour and per liter of reaction mixture.
• the reaction mixture is concentrated by distillation of the volatile products at 90 ° C, under a pressure of 1 kPa; a mixture is thus obtained which is subjected to a refining operation.
• the device used consists of a metal cylinder, with an internal diameter of 45 mm and a height of 65 cm, closed at its base by a pneumatic valve of small volume and provided at its top with a screwed cover crossed by two temperature probes and a nitrogen supply.
• the whole is surrounded by a double envelope allowing the organized circulation of a heat-transfer fluid at controlled temperature
• This reaction mixture in the liquid state at 131 ° C. is loaded into the apparatus being at this same temperature.
• the temperature is gradually lowered using the coolant to 40 ° C in 9 hours: this is the crystallization phase.
• the valve of the apparatus is opened and the draining phase is carried out at constant temperature for 3 h: the draining fraction thus representing 20% by weight by weight of the charged reaction mixture is recovered.
• the temperature then gradually increased to 138 ° C in 11 hours; during this PT phase, a PT fraction representing 28% by weight by weight of the charged reaction mixture is recovered.
• the raffinate therefore contains 76% of adipic acid and only 9% of iridium and iodine present in the reaction mixture resulting from the hydroxycarbonylation reaction.
• the draining fraction contains 45% of the iridium and iodine and 3% of the adipic acid of the reaction mixture, while the penetrant fraction contains 46% of the iridium and iodine and 21% adipic acid.
• the racking consisting of all the draining and bleeding fractions therefore contains 91% of iridium and iodine with 24% of the adipic acid of the reaction mixture.
• Different partitions of the fractions and of the raffinate make it possible either to minimize the amount of adipic acid present in the racking, or to increase the recovery rate of iridium and iodine according to the preferred separation criterion.
• Example 2 100 g of the draining fraction obtained in Example 2 are recycled. To it is added pentene-3-oic acid and water, so as to have an initial reaction mixture having the same concentration of Ir and in HI than the initial mixture used in Example 1, that is to say 3.3 mmol / l of lr and 8.5 mmol / l of HI.
• the hydroxycarbonylation is carried out as described in Example 1. After 40 min of reaction, corresponding to the consumption of the water introduced, the autoclave is cooled and the various constituents of the final reaction mixture are assayed.
• the linearity rate expressed as the percentage ratio of A1 formed on all of the diacids A1, A2 and A3 formed, is 80%.
• the reaction rate (calculated over 20 min of CO absorption) is 4.4 moles of CO absorbed per hour and per liter of reaction mixture.
• the kinetics being of order 1 relative to P3, there is therefore a catalyst activity identical to that observed in Example 1 (volume CO absorption / amount of P3 engaged).

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Crystallography & Structural Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Applications Claiming Priority (3)

Publications (2)

Family

ID=9434963

Family Applications (1)

Country Status (18)

Families Citing this family (9)

Family Cites Families (11)

• 1992
  • 1992-10-22 FR FR9212913A patent/FR2697247B1/fr not_active Expired - Fee Related
• 1993
  • 1993-10-04 TW TW082108170A patent/TW252102B/zh active
  • 1993-10-19 WO PCT/FR1993/001028 patent/WO1994008939A1/fr active IP Right Grant
  • 1993-10-19 EP EP93924095A patent/EP0665828B1/fr not_active Expired - Lifetime
  • 1993-10-19 US US08/424,335 patent/US6008408A/en not_active Expired - Fee Related
  • 1993-10-19 DE DE69310193T patent/DE69310193T2/de not_active Expired - Fee Related
  • 1993-10-19 KR KR1019950701488A patent/KR0185232B1/ko not_active Expired - Fee Related
  • 1993-10-19 ES ES93924095T patent/ES2100575T3/es not_active Expired - Lifetime
  • 1993-10-19 CZ CZ19951013A patent/CZ286694B6/cs not_active IP Right Cessation
  • 1993-10-19 JP JP6509714A patent/JP2895233B2/ja not_active Expired - Lifetime
  • 1993-10-19 BR BR9307284A patent/BR9307284A/pt not_active IP Right Cessation
  • 1993-10-19 CA CA002146975A patent/CA2146975A1/fr not_active Abandoned
  • 1993-10-19 PL PL93308300A patent/PL175043B1/pl not_active IP Right Cessation
  • 1993-10-19 RU RU95109575A patent/RU2119477C1/ru not_active IP Right Cessation
  • 1993-10-19 SK SK518-95A patent/SK280442B6/sk unknown
  • 1993-10-19 SG SG1996008354A patent/SG70989A1/en unknown
  • 1993-10-19 UA UA95038271A patent/UA44228C2/uk unknown
  • 1993-10-21 CN CN93119171A patent/CN1034660C/zh not_active Expired - Fee Related

Also Published As

Similar Documents

Legal Events